Production of molding resins



Patented Nov. 3, 1 936 PATENT OFFICE 2,059,526 PRODUCTION or MOLDINGRESINS Kenneth M..Irey, Ridgefield Park, N. 3., and Lloyd G. Swallen,Terre Haute, Ind., assignors to Resinox Corporation, New York, N. Y., acorporation of Delaware No Drawing. Application July 13, 1933,

' Serial'No.680,230

9 Claims. (oi. 260-4) Our present invention relates to improvements inand relating to the manufacture of molding resins, and has particularreference to the manufacture of this type of resin from phenolic bodies,ketones and aldehydes, and more particularly, from phenol, acetone andformaldehyde.

In a co-pending application Serial No. 571,863, by K. M. Irey, forOil-soluble resins, filed October 29, 19.31, now matured into U. S.Patent 1,948,469, there has been described a method of I makingoil-soluble resins by first reacting a phenol and a ketone in such amanner as to give a mixture of a bis-[4-hydroxy-aryll-dialkyl methaneand a bis-li-hydroxy-aryll-dialkyl methaneketone condensation product inapproximately equal proportions. After removal of the catalyst andexcess phenol, this intermediate material is next reacted under suitableconditions with less than 0.5, and preferably with from 0.25 to 0.35mol. .of an aldehyde per mol. of phenol reacted in producing the saidmixed intermediate so as to give a resinous body which is soluble in oiland having in general the various properties necessary for theproduction of an oil varnish.

We have now made the discovery that by suitably modifying theproportions of the reactants and the operating conditions a resin may beobtained possessing characteristics which made it highly suitable forthe production of many varieties of molded articles for which previouslyknown types of resins may not be conveniently employed. The method ofproducing our new molding resin may be illustrated by the followingspecific-examples.

The first step in the operation involves the preparation of a mixture ofbis-[hydroxy-arylldialkyl methane and bis- [hydroxy-aryl] -dialkylmethane-keton condensation product, such as, for example, a mixture ofbis-[4-hydroxyary1ldialkyl methane and bis-[4-hydroxy-aryll-dialkylmethane-ketone condensation product. These materials may be preparedseparately and mixed in suitable proportions. Preferably, however, asuitable mixture of the two compounds is obtained in a single operationof the following character: Two and one-half mols phenol are melted andmixed with one mol. of acetone in a reaction vessel provided with coilsor other suitable means for heating or cooling the contents thereof.-From 5 to 6% of hydrochloric acid (32%) based on the weight of thephenol, is next added to the reaction mixture and the latter thensuitably cooled or heated so that a reaction temperature ofapproximately -82 C.

After the completion of the reaction the hydrochloric acid catalyst isremoved by neutralizing with an aqueous solution of an alkali, such aslime water and the resulting salt water layer removed from the reactionmixture which is sub- 5 jected' to steam distillation in order torecover unreacted phenol, approximately 30% of the original phenol beingrecovered at this point. The resulting reaction mixture is composed of amixture of approximately 55-65% beta.beta- 10 'bis-[hydroxy phenyl]propane and approximately 45 -35 beta.beta-bis- [hydroxy-phenyllpropane-acetone condensation product. The 4- hydroxy-phenyl typecompound appears to be chiefly formed.

When crude phenol, composed of say phenol and 10% cresols is used as thereactant in place of pure phenol, a mixture of-the correspondinghydroxy-aryl and i-hydroxy-aryl type compounds are obtained. Forcommercial scale 20 operations, the use of crude phenol naturally hascertain advantages.

lBetabeta-bis- [i-hydroxy-phenyl] -propane is a white crystallinematerial with a melting point of -154 C. Betabeta-bis[i-hydroxy-phenyll- 25 propane-acetone condensation product is a reddishcolored material having a melting point around 50 C.

The reaction described above may be regulated so as to vary the relativeproportions of beta.beta- 30 bis-[4= hydroxy-phenyll-propane andbeta.betabis-[i-hydroxy-phenyl]-propane--acetone condensation product inthe reaction product. The proportion of the latter in the reactionproduct may generally be increased by using a higher as reactiontemperature and a longer time of reaction.

If desired, the above mentioned materials may be prepared separately andthen mixed in approximately equal proportions to give the inter- 4.0mediate necessary for the production of our new molding resin.Beta.beta-bis-[4hydroxyphenyll-propane and its homologues may beprepared, for example, by the method described by W. A. Beatty in U. S.Patent No. 1,225,748, granted 45 March 15, 1917.

Betahta-bis-[-hydroxy phenyllpropaneacetone condensation product and itshomologues may be prepared, for example, by reacting equimolecularproportions of phenol and acetone in 50 the presence of hydrochloricacid as a catalyst and at a temperature of 70-80" C. for a period ofabout 48 hours or at room temperature for several days, the unreactedphenol and catalyst being removed at the end of the operation and 65formaldehyde in the presence of a catalyst. One

mol. of intermediate" is placed in the reaction vessel, melted, cooledto a temperature of approximately 85-90 0., and approximately 1.075 molsof formaldehyde per mol. of residualphenol in said intermediate in theform of an aqueous solution are added. The resulting mixture is thensubjected to additional cooling, if necessary to attain a temperature ofapproximately 50 C. An aqueous solution of approximately 0.016 mol. ofbarium hydroxide is then added to the reaction mixture to serve as acatalyst. The heat generated by the reaction is generally sufficient tocomplete the reaction and ordinarily it is advisable to cool the mixtureduring the early stage of the reaction in order to prevent thetemperature from rising too high. The temperature is preferablymaintained within the range 50 to 85 C. until a sample removed'from thereaction vessel for testing is converted to a dry rubber-like state whenheated on a hot plate at 150 C. for 75-80 seconds.

When the reaction has progressed to the desired point the reactionmixture is dehydrated under vacuo, the temperature still beingmaintained below C. and preferably below 75 G. Since the final resin hasa high melting point, it is desirable to raise the temperature of theresin rapidly near the end of the operation in order to get as much ofthe excess water as possible off. This may be accomplished by decreasingthe vacuum. Near the end of the operation the temperature, vacuum, and.time of heating should be carefully watched in order to remove as muchwater as possible and at the same time preventexcessive polymerization.The finished resin may be handled in the customary manner.

The synthetic resin obtained by the procedure just described is verylight in color, enabling it to be used for purposes for which othersynthetic resins may not be satisfactorily employed on account of theirdarker color. of equal, if not greater, importance is the fact that ournew resin does not turn yellow or darken on exposure to light, as is thecase with other synthetic resins which are originally light in color.This property enables our new resin to be used in the production ofplasticsof many and delicate shades of colors. It is particularly bettersuited for such purposes than the ordinary phenol-formaldehyde andformaldehyde-urea synthetic resins. Further advantages in our new resinare its low degree of 'hydroscopicity and high strength, its strengthbeing approximately 20% higher than that of the usual grades ofphenol-formaldehyde resins. Rapid and satisfactory cures also may beobtained without the aid of hardening agents such as hexamethylenetetramine.

It is understood, of course, that our invention is not limited to theexact procedure of the specific example cited above but that the usualvariations and equivalents which would occur to one skilled in the artmay be employed. For example, other compounds having characteristicssimilar to ace-- tone, phenol, formaldehyde and barium hydroxide willreadily suggest themselves as equivalents of these substances. Examplesof other such ketones are: methyl ethyl ketone, methyl propyl ketone,diethyl ketone. Otheraldehydes which may be regarded as equivalents offormaldehyde are: acetaldehyde, butyraldehyde, propionaldehyde, etc. Thecresols are examples of other phenolic bodies similar to phenol. For thebarium hydroxide used as catalyst we may substitute other alkaline earthhydroxides such as calcium hydroxide or less desirably sodium hydroxideas other alkaline material or acidic materials such as sulphuric oroxalic acids. It is understood also that although the hydroxy-phenyl and4-hydroxyphenyl type compounds have been referred to specifically in theexample, we may employ with satisfactory results the correspondinghydrox-yaryl and 4-hydroxy-aryl type compounds.

The proportions of the reactants also may be I varied within certainlimits without materially affecting the character of the final product.For example, whileapproximately 0.60 mol. of aldehyde per mol.of phenolreacted in preparing the phenolketone condensation product appears to bethe least amount of aldehyde which may be used to give a satisfactoryproduct, this amount may be very materially increased. 1.075 mols ofaldehyde per mol. of phenol gives a product of highly desirablecharacter. Aldehyde to the extent of even 2.0 or more mols per mol. ofresidual phenol may be employed but in general such amounts are en- Ytirely unnecessary and will be largely unreactedor lost.

The proportions of bis-[hydroxy-aryll-dialkyl methane tobls-[hydroxy-aryl]-dialkyl methane-ketone condensation product may alsobe varied over rather wide limits. We prefer, however, to use anintermediate containing approximately 60% of the former to 40% of thelatter.

Now having described our invention, what we claim is:

1. -In a process of producing a quick curing infusible molding resin,the step which comprises reacting a mixture comprising essentially, asmajor components, bis-[hydroxy-aryll-dialkyl methane andbis-[hydroxyary1]-dialkyl methaneketone condensation product with inexcess of 0.6 mol. of an aldehyde per mol. of phenolic body reacted inproducing said mixture of bis- [hydroxy-aryll-dialkyl methane andbis-[hydroxy-aryll-dialkyl methane-ketone condensation product.

2. In a process of producing a quick curing infusible molding resin, thestep which comprises reacting a'mixture comprising essentially, as majorcomponents, bis-[4-hydroxy-aryll-dialkvl methane andbis-[4-hydroxy-aryl] -dialkyl methane-ketone condensation product in thepresence of an alkali catalyst, with in excess of 0.60

mol. of an aldehyde per mol. of phenolic body phenyll-propane andbeta.beta-bis-[4-hydroxyphenyll-propane--acetone condensation productwith in excess of 0.60 mol. of formaldehyde per mol. of phenol reactedin producing said mixture of beta.beta-bis- [4-hydroxy-phenyl] -propaneand beta. beta-bis- [4-hydroxy-pheny1] -propaneacetone condensationproduct.

4. In a process of producing a quick curing infusible molding resin, thestep which comprises reacting a mixture comprising essentially, as majorcomponents, beta.beta-bi s.-[4-hydroxyphenyll-propane andbeta.beta-bis-[4-hydroxyphenyll-propane-acetone condensation product inthe presence of an alkaline earth hydroxide with in excess of 0.60 mol.of formaldehyde per mol. of phenol reacted in producing said mixture ofbeta.beta-bis [fl-hydroxy-phenyl] -propane and beta .beta-bis- [4hydroxy-phenyl] -propane acetone condensation product.

5. In a process of producing a quick curing infusible molding resin, thestep which comprises reacting a mixture comprising essentially, as majorcomponents, beta.beta-bis-[4-hydroxyphenyll-propane andbeta.beta-bis-[-hydroxyphenyll-propane -acetone condensation productwith approximately 1.075 mols of formaldehyde prising essentially, asmajor components, bis- [hydroxy-aryll-dialkyl methane andbis-[hydroxy-aryll-dialkyl methane-ketone condensation product with inexcess of 0.6 mol. of an aldehyde per mol. of phenolic body reacted inproducing said mixture of, bis-[hydroxy-aryll-dialkyl methane andbis-'[hydroxy-aryll-dialkyl methane-ketone condensation product.

'7. A quick curing infusible molding resin comprising the reactionproduct of a mixture comprising essentially, as major components, bis-[4-hydroxy-aryll-dialkyl methane and bis-[4- hydroxy-aryll-diakylmethane-ketone condensation product with in excess of 0.6 mol. of analdehyde per mol. of phenolic body reacted in producing said mixture ofbis-[4-hydroxy-arylldialkyl methane and bis-[4-hydroxy-aryll-dialkylmethane-ketone condensation product.

8. A quick curing infusible molding resin comprising the reactionproduct of a mixture comprising essentially, as major components, beta.-beta-bis-[4-hydroxy-aryll-propane and beta.- beta bis [4 hydroxyaryl]-propane-acetone condensation product with in excess of 0.6 mol. offormaldehyde per mol. of phenolic body reacted in producing said mixtureof beta.beta-bis-[4- hydroxyaryl -propane and beta.beta-bis- [4-hydroxyaryl] propane acetone condensation product. I

9. A quick curing infusible molding resin comprising the reactionproduct of a mixture comprising essentially, as major components, beta.-

' beta-bis- [hydroxy-aryll -propane and beta..b'etabis- [hydroxy-aryll-propane-acetone condensation product with approximately 1.075 mole offormaldehyde per mol. of phenolic body reacted in producing said mixtureof beta.beta-bis-[hydroxy aryl] propane and beta.beta-bis-[hydroxy aryl]propane acetone condensation product.

KENNETH M. IREY.

LLOYD C. SWAILEN.

